CN109252292A - Double anisotropic conductive flexible compound films of green emitting and preparation method thereof - Google Patents

Double anisotropic conductive flexible compound films of green emitting and preparation method thereof Download PDF

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CN109252292A
CN109252292A CN201810295539.2A CN201810295539A CN109252292A CN 109252292 A CN109252292 A CN 109252292A CN 201810295539 A CN201810295539 A CN 201810295539A CN 109252292 A CN109252292 A CN 109252292A
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anisotropic conductive
pmma
green emitting
nanobelt
film
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CN109252292B (en
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于文生
马千里
刘靖宇
田娇
李丹
奚雪
杨颖�
王进贤
刘桂霞
宋超
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Changchun University of Science and Technology
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    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0069—Electro-spinning characterised by the electro-spinning apparatus characterised by the spinning section, e.g. capillary tube, protrusion or pin
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
    • D01D5/0084—Coating by electro-spinning, i.e. the electro-spun fibres are not removed from the collecting device but remain integral with it, e.g. coating of prostheses
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The present invention relates to double anisotropic conductive flexible compound films of green emitting and preparation method thereof, belong to technical field of nanometer material preparation.The present invention includes five steps: (1) precipitation method preparation Tb (BA)3(phen) complex；(2) polymetylmethacrylate is prepared；(3) spinning solution is prepared；(4) [Tb (BA) is prepared3Phen/PMMA] // [PANI/PMMA] anisotropic conductive green emitting Janus nano-band array film, it is prepared using double-spinneret electrostatic spinning technique arranged side by side；(5) the double anisotropic conductive flexible compound films of green emitting are prepared, are prepared using secondary electrospinning.Prepared flexible compound film has good green emitting and double anisotropic conductive characteristics simultaneously.Method of the invention is simple and easy, can produce in batches, and this novel nano structural material has broad application prospects.

Description

Double anisotropic conductive flexible compound films of green emitting and preparation method thereof
Technical field
The present invention relates to technical field of nanometer material preparation, and it is multiple in particular relate to the double anisotropic conductive flexibilities of green emitting Close film and preparation method thereof.
Background technique
Anisotropic conductive film is a kind of novel electronic component interconnecting material, it have electric conductivity in one direction and Insulating properties on other directions, be widely used in Electronic Packaging, chip is fixed and electrode bonding etc. fields.It is led by it Electric direction classification, can be divided into following two class: I type anisotropic conductive film: this anisotropic conductive film is along the thickness side of film It to conduction, and insulate along film surface direction, the technology of preparing of this anisotropic conductive film is highly developed, and by widely Using in the electronic device；II type anisotropic conductive film: this anisotropic conductive film has not along the different directions of its film surface With electric conductivity, usually in two vertical direction of film surface, a direction conduction, another direction insulation, have it is each to Anisotropic electric conductivity.The research of II type anisotropic conductive film is still in the laboratory exploratory stage, be not implemented industrialized production and Using.
Janus material refers to two kinds of chemical compositions or a kind of chemical composition but structure difference has clearly in same system Partitioned organization, thus there is double properties such as hydrophilic/hydrophobic, polar/non-polar, shine/conductive, horizontal direction is conductive/vertical Direction conduction etc. is one of forward position, hot research direction of materials science field.Janus nanobelt refers to two kinds of chemical compositions There is clear partitioned organization in same nanobelt, there is two or more property, shine as the side of nanobelt has The other side of function, nanobelt has conducting function, if these Janus nanobelts can be determined using special reception device To arrangement, Janus nano-band array film is formed, this array films have luminous and conduction difunctional.
Rare earth metal terbium coordination compound Tb (BA)3Phen, Tb3+For terbium ion, BA is benzoic acid, and phen is phenanthroline, because The unique electron configuration of terbium ion and become it is unique can green luminescent material, as luminous intensity is high, stability is good, glimmering The advantages that quantum yield is high, monochromaticjty is good, is a kind of widely applied green fluorescent material.Polyaniline PANI is easy due to it The advantages that synthesis, good conductivity height and environmental stability, have become one of the hot spot of conducting polymer area research.People are The polyaniline PANI of the one-dimensional nano structures such as nano wire, nanometer rods, nanotube and nanofiber is synthesized.
Existing research is it has been proved that as dark colour electrically conductive polyaniline PANI and rare earth compounding Tb (BA)3Phen is straight Its illumination effect can be significantly reduced by connecing mixing, therefore obtain Tb (BA)3The good illumination effect of phen, it is necessary to make Tb (BA)3Phen and PANI realization efficiently separates.If conductive polymer polyanilinc PANI mixed with polymetylmethacrylate Be prepared into nanobelt, conductive PANI be it is continuous, ensure that its high conductivity, as the side of Janus nanobelt, then the side It is conductive, and by Tb (BA)3Phen, which is scattered in macromolecule PMMA, is prepared into nanobelt, as the another of Janus nanobelt Side, then the side has the characteristics of luminescence, forms [Tb (BA)3Phen/PMMA] // [PANI/PMMA] green emitting conduction is difunctional Janus nanobelt, so as to so that electrically conductive polyaniline PANI and Tb (BA)3Phen, which is realized, to be efficiently separated, and good hair is obtained Light effect.If can also obtain Janus nano-band array film using special device, be led in this way along nanobelt length direction It is electrically strong, and along perpendicular on nanobelt direction, due to there is nonconducting Tb (BA)3Phen/PMMA structural unit exists, and makes Obtaining the direction has insulating properties, to have anisotropic conductive, can be obtained by [Tb (BA) in this way3phen/PMMA]// [PANI/PMMA] anisotropic conductive green fluorescence Janus nano-band array film, recycles secondary electrospinning, constructs same Janus nano-band array film, this two array films are firmly combined together to form up-down structure, obtain composite construction film, In the upper layer and lower layer film of this composite construction film, nanobelt length direction is vertical namely conducting direction is vertical, therefore, this Composite membrane has the function of double anisotropic conductive characteristics and green emitting.Such special nano-structure film, will be in the following nanometer It is with important application prospects in structure devices and medical diagnosis treatment.Have not yet to see relevant document report.
One related electrospinning process (electrospinning) of the U.S. Patent Publication of Patent No. 1975504 Technical solution, this method is a kind of effective ways for preparing continuous micro nanometer fiber with macro length, by Formhals was proposed first in 1934.This method is mainly used to prepare high polymer nanometer fiber, it is characterized in that making electrification Polymer solution or melt is sprayed by the traction of electrostatic force by nozzle in electrostatic field, invests the receiving screen on opposite, thus real Existing wire drawing, then, solvent evaporation or melt are cooled to room temperature and solidify at normal temperature, obtain micro nanometer fiber.Nearly more than ten years Since, occur preparing inorganic compound such as oxidate nano fibre using electrospinning process in inorfil preparation technical field The technical solution of dimension, the oxide include TiO2、ZrO2、Y2O3、Y2O3:RE3+(RE3+=Eu3+、Tb3+、Er3+、Yb3+/Er3 +)、NiO、Co3O4、Mn2O3、Mn3O4、CuO、SiO2、Al2O3、V2O5、ZnO、Nb2O5、MoO3、CeO2、LaMO3(M=Fe, Cr, Mn, Co、Ni、Al)、Y3Al5O12、La2Zr2O7Equal metal oxides and composite oxide of metal.Q.Z.Yu, et al. use Static Spinning Silk technology is prepared for polyaniline PANI nanofiber [Mater.Sci.Eng.B, 2008,150,70-76].Someone utilizes electrostatic Spining technology is successfully prepared high molecular nanometer band [Materials Letters, 2007,61:2325-2328；Journal of Polymer Science:Part B:Polymer Physics,2001,39:2598–2606].Someone is organised using tin Object is closed, is combined using electrostatic spinning technique with metallo-organic compound decomposition technique and is prepared for porous SnO2Nanobelt [Nanotechnology,2007,18:435704].It is multiple that someone is prepared for PEO/ stannic hydroxide using electrostatic spinning technique first Nanobelt is closed, is roasted to have obtained porous SnO2Nanobelt [J.Am.Ceram.Soc., 2008,91 (1): 257-262].Dong Phase court of a feudal ruler etc. using electrostatic spinning technique be prepared for trifluorides nanobelt [Chinese invention patent, application number: 201010108039.7], titanium dioxide nano-belts [Chinese invention patent, grant number: ZL200810050948.2] and Gd3Ga5O12:Eu3+Porous nano-belt [Chemical Journal of Chinese Universities, 2010,31 (7), 1291-1296].Dong Xiangting etc. uses single A spinning head is prepared for PAN/Eu (BA) using electrostatic spinning technique3Phen recombination luminescence nanofiber [New Chemical Materials, 2008,36(9),49-52].Dong Xiangting etc. is prepared for Eu (BA) using single spinning head, using electrostatic spinning technique3phen/ The difunctional composite nano fiber of PANI/PVP photoelectricity [Chemical Journal of Chinese Universities, 2012,33 (8), 1657-1662].Dong Xiangting Eu (BA) is prepared for Deng using electrostatic spinning technique3Phen/PVP//PANI/PVP photoelectricity double function two-stranded parallel nanometer fiber bundle [national inventing patent, application number: 201210407369.5].Dong Xiangting etc. is prepared for single anisotropy using electrostatic spinning technique Conductive-magnetic-light three functions Janus nano-band array (national inventing patent, grant number: 201410795673.0； Adv.Funct.Mater.,2015,25,2436-2443).Green emitting pair is prepared respectively using electrostatic spinning technique currently, having no The relevant report of anisotropy conductive flexible composite membrane.
When preparing nano material using electrostatic spinning technique, the type of raw material, the molecular weight of high polymer templates, spinning solution Composition, spinning process parameter and spinning head structure the morphology and size of final products is all had a major impact.The present invention adopts With electrostatic spinning technique, spinning head be close together by the identical syringe needle of two truncated diameters of 12# form it is arranged side by side double Spinning head, with Tb (BA)3Phen complex, PMMA, N,N-dimethylformamide DMF and chloroform CHCl3Mixed liquor be a kind of spinning Silk liquid, by aniline, camphorsulfonic acid, ammonium persulfate, PMMA, DMF, CHCl3Mixing, is constituted another after aniline polymerization is at polyaniline Kind spinning solution, the viscosity for controlling spinning solution is most important, under optimal process conditions, obtains [Tb (BA)3phen/PMMA]// [PANI/PMMA] anisotropic conductive green emitting Janus nano-band array film, recycles secondary electrospinning, constructs same Janus nano-band array film, this two array films are firmly combined together to form up-down structure, obtain composite construction film, In the upper layer and lower layer of this composite construction film, nanobelt length direction is vertical namely conducting direction is vertical, to be had The flexible compound film of double anisotropic conductive characteristics and green emitting function.
Summary of the invention
Macromolecule, metal oxide, metal fluoride and metal are prepared for using electrostatic spinning technique in the background technology Composite oxides nanofiber and nanobelt, PAN/Eu (BA)3Phen recombination luminescence nanofiber, polyaniline PANI Nanowire Dimension, Eu (BA)3The difunctional composite nano fiber of phen/PANI/PVP photoelectricity, Eu (BA)3Phen/PVP//PANI/PVP photoelectricity is double Two bursts of function parallel bundles of nanofibers and the magnetic-light three functions Janus nano-band array of single anisotropic conductive-.Used original Material, template, solvent and final target product and method of the invention are different.The present invention uses electrostatic spinning technique, [Tb (BA) is prepared for using double-spinneret arranged side by side3Phen/PMMA] // [PANI/PMMA] anisotropic conductive green emitting Janus nano-band array film, recycles secondary electrospinning, constructs same Janus nano-band array film, this two array films It is firmly combined together to form up-down structure, obtains the double anisotropic conductive flexible compound films of green emitting, be anisotropy Conducting membrane material field increases a kind of new structural conductive film.
The invention is realized in this way preparing Tb (BA) using the precipitation method first3Phen complex, with Tb (BA)3Phen, PMMA, DMF and CHCl3Mixed liquor as a kind of spinning solution, by aniline, camphorsulfonic acid, ammonium persulfate, PMMA, DMF And CHCl3Mixing, constitutes another spinning solution after aniline polymerization is at polyaniline, and the viscosity for controlling spinning solution is most important.It adopts Electrostatic spinning is carried out with double-spinneret arranged side by side, using electrostatic spinning technique, under optimal process conditions, obtains [Tb (BA)3Phen/PMMA] // [PANI/PMMA] anisotropic conductive green emitting Janus nano-band array film, recycle secondary electrospinning Technology constructs same Janus nano-band array film, this two array films are firmly combined together to form up-down structure, obtains To the double anisotropic conductive flexible compound films of green emitting.It the steps include:
(1) precipitation method preparation Tb (BA)3Phen complex
By 1.8650g Tb4O7It is dissolved in 15mL concentrated nitric acid, heating is evaporated to obtain Tb (NO3)3It is anhydrous that 20mL is added in crystal Ethyl alcohol is configured to Tb (NO3)3Ethanol solution；It is anhydrous that 3.6640g benzoic acid and 1.8000g phenanthroline are added to 200mL Mixed ligand solution is configured in ethyl alcohol, in the case where being stirred continuously by Tb (NO3)3Ethanol solution be added dropwise to mixing and match In liquid solution, dense NH is added3·H2O adjusts pH between 6.5-7.0, after being heated to 60 DEG C, reacts 3h, gained precipitates successively With water and ethanol washing 3 times, 12h is finally dried at 60 DEG C in drying box, obtains Tb (BA)3Phen complex；
(2) polymetylmethacrylate is prepared
100g methyl methacrylate MMA and 0.1g dibenzoyl peroxide BPO is weighed, is added to reflux unit In 250mL three-necked bottle and stir evenly, by above-mentioned solution 90-95 DEG C at a temperature of be vigorously stirred and be back to solution and have centainly Viscosity stops heating and naturally cools to room temperature after its viscosity is close with glycerol while continuing stirring, later will be above-mentioned Infusion is into test tube, influx height 5-7cm, and 2h is stood after perfusion to invisible spectro solution does not have bubble, then Above-mentioned test tube is transferred in 50 DEG C of drying boxes and places 48h, invisible spectro liquid hardening is transparent solid, finally by drying box Temperature improves to 110 DEG C and keeps the temperature 2h, terminates polymerization reaction, then cooled to room temperature, obtains poly-methyl methacrylate Ester PMMA；
(3) spinning solution is prepared
1.0000g PMMA and 0.15000g Tb is added in the in the mixed solvent of 12.0000g chloroform and 2.0000g DMF (BA)3Phen complex simultaneously stirs for 24 hours, obtains a spinning solution, has the function of green emitting；In 14.0000g chloroform and 1.0000g PMMA is added in the in the mixed solvent of 2.0000g DMF, and stirring 2h obtains uniform colloidal fluid, by 0.3000g aniline It is added in above-mentioned colloidal fluid and after stirring 2h with 0.5618g camphorsulfonic acid, 0.4411g ammonium persulfate is added and stirs 2h, then Solution is put into 5 DEG C of cold compartment of refrigerator for 24 hours, obtains another spinning solution, there is conducting function；
(4) [Tb (BA) is prepared3Phen/PMMA] // [PANI/PMMA] anisotropic conductive green emitting Janus nanobelt Array films
The 5mL syringe that truncated 12# stainless steel syringe needle is all had using two difference is distinguished two stainless pin heads curved Bent 30 ° of angles keep two needle points closely parallel, and make on two parallel stainless steel syringe needles using a 1mL plastic spray gun headgear The tip of two stainless steel syringe needles is in the middle section of plastic spray gun head, and two spinning solutions respectively take 3mL to be injected separately into two In syringe, using perpendicular spray mode, reception device is a horizontal positioned long 20cm, and the cylindrical aluminum that diameter is 7cm turns Cylinder, revolving speed 1200r/min, other spinning parameters are spinning voltage 6kV, and needle point and rotating cylinder spacing are 13cm, environment temperature It is 20-25 DEG C, relative humidity 20%-30% obtains [Tb (BA) after spinning solution exhausts3phen/PMMA]//[PANI/ PMMA] anisotropic conductive green emitting Janus nano-band array film；
(5) the double anisotropic conductive flexible compound films of green emitting are prepared
By [the Tb (BA)3Phen/PMMA] // Janus nanometers of [PANI/PMMA] anisotropic conductive green emitting Band array films are removed from aluminum rotating cylinder, are cut out to be 3.5cm, perpendicular to nanometer strip length along Janus nanobelt length direction Direction is the rectangle of 3.0cm, displays Janus nanobelt with adhesive tape after being rotated by 90 ° and is fixed on aluminium at left and right sides of film On rotating cylinder processed, the length direction of nanobelt and the axial direction of rotating cylinder are consistent at this time, and left and right sides adhesive tape covers the area of sample It is all 3 × 0.25cm2, the area of the Janus nano-band array film of exposing is 3 × 3cm2, as the receiving plane of secondary electrospinning film, Spinning solution dosage and spinning parameter are identical as first time electro-spinning process, carry out secondary electrospinning, by film from aluminum after the completion of spinning It removes and is cut on rotating cylinder, obtain 3 × 3cm2The double anisotropic conductive flexible compound films of green emitting.
The area of the double anisotropic conductive flexible compound films of prepared green emitting is 3 × 3cm in the above process2, by [Tb(BA)3Phen/PMMA] it is compound above and below // [PANI/PMMA] anisotropic conductive green emitting Janus nano-band array film It forms, the thickness of upper lower film is about 212 μm, by [the Tb (BA) aligned in upper lower film3phen/PMMA]//[PANI/ PMMA] Janus nanobelt composition, the width of Janus nanobelt is 6.64 ± 0.01 μm, with a thickness of 930nm, in the upper of composite membrane In lower two membranes, nanobelt length direction is vertical namely conducting direction is vertical, in upper layer film, along nanobelt length direction Electric conductivity is strong, and conductance is 1.62 × 10-8S, and along weak perpendicular to nanobelt length direction electric conductivity, conductance is 1.28 × 10- 12S has anisotropic conductive, strong along nanobelt length direction electric conductivity in lower membrane, and conductance is 1.16 × 10- 8S, and along weak perpendicular to nanobelt length direction electric conductivity, conductance is 1.27 × 10-12S has anisotropic conductive, whole A composite membrane has double anisotropic conductives；Under the ultraviolet excitation of 291nm, launches main peak and be located at the bright of 544nm Green light；Prepared flexible compound film has the function of good green emitting and double anisotropic conductives, realizes goal of the invention.
Detailed description of the invention
Fig. 1 is the SEM photograph of the double anisotropic conductive flexible compound films of green emitting, which also serves as Figure of abstract；
Fig. 2 is the SEM photograph of Janus nano-band array film in the double anisotropic conductive flexible compound films of green emitting；
Fig. 3 is the width distribution histogram of Janus nanobelt in the double anisotropic conductive flexible compound films of green emitting；
Fig. 4 is the line analysis energy dispersive spectrum of Janus nanobelt in the double anisotropic conductive flexible compound films of green emitting Figure；
Fig. 5 is that the optical microscopy of single Janus nanobelt in the double anisotropic conductive flexible compound films of green emitting shines Piece；
Fig. 6 is the exciting light spectrogram of the double anisotropic conductive flexible compound films of green emitting；
Fig. 7 is the launching light spectrogram of the double anisotropic conductive flexible compound films of green emitting；
Fig. 8 is the chromaticity coordinates figure of the double anisotropic conductive flexible compound films of green emitting.
Specific embodiment
Terbium oxide Tb selected by the present invention4O7Purity be 99.99%, n,N-Dimethylformamide, chloroform, nitric acid, benzene Formic acid, phenanthroline, dehydrated alcohol, ammonium hydroxide, aniline, camphorsulfonic acid, dibenzoyl peroxide, methyl methacrylate, over cure Sour ammonium is commercially available analysis net product；The self-control of deionized water laboratory；Glass apparatus and equipment used is commonly used in laboratory Instrument and equipment.
Embodiment: by 1.8650g Tb4O7It is dissolved in 15mL concentrated nitric acid, heating is evaporated to obtain Tb (NO3)3Crystal is added 20mL dehydrated alcohol is configured to Tb (NO3)3Ethanol solution；3.6640g benzoic acid and 1.8000g phenanthroline are added to Mixed ligand solution is configured in 200mL dehydrated alcohol, in the case where being stirred continuously by Tb (NO3)3Ethanol solution add dropwise Into mixed ligand solution, dense NH is added3·H2O adjusts pH between 6.5-7.0, after being heated to 60 DEG C, reacts 3h, gained Precipitating successively uses water and ethanol washing 3 times, finally dries 12h at 60 DEG C in drying box, obtains Tb (BA)3Phen complex； 100g methyl methacrylate MMA and 0.1g dibenzoyl peroxide BPO is weighed, the 250mL tri- with reflux unit is added to In neck bottle and stir evenly, by above-mentioned solution 90-95 DEG C at a temperature of be vigorously stirred and be back to solution and have certain viscosity, when After its viscosity is close with glycerol, stops heating while continuing stirring and naturally cool to room temperature, later fill above-mentioned solution It infuses in test tube, influx height 5-7cm, 2h is stood after perfusion to invisible spectro solution does not have bubble, then will be above-mentioned Test tube, which is transferred in 50 DEG C of drying boxes, places 48h, and invisible spectro liquid hardening is transparent solid, finally proposes drying box temperature Up to 110 DEG C and 2h is kept the temperature, terminates polymerization reaction, then cooled to room temperature, obtain polymetylmethacrylate； 1.0000g PMMA and 0.15000g Tb (BA) is added in the in the mixed solvent of 12.0000g chloroform and 2.0000g DMF3phen Complex simultaneously stirs for 24 hours, obtains a spinning solution, has the function of green emitting；In 14.0000g chloroform and 2.0000g DMF 1.0000g PMMA is added in the mixed solvent, and stirring 2h obtains uniform colloidal fluid, by 0.3000g aniline and 0.5618g camphor Sulfonic acid is added in above-mentioned colloidal fluid and after stirring 2h, and 0.4411g ammonium persulfate is added and stirs 2h, solution is then put into 5 DEG C Cold compartment of refrigerator in for 24 hours, obtain another spinning solution, have conducting function；Truncated 12# is all had not using two difference Two stainless pin heads are bent 30 ° of angles by the 5mL syringe of rust steel needle head respectively, keep two needle points closely parallel, and use one 1mL plastic spray gun headgear makes the tip of two stainless steel syringe needles be in plastic spray gun head on two parallel stainless steel syringe needles Middle section, two spinning solutions respectively take 3ml to be injected separately into two syringes, and using perpendicular spray mode, reception device is one Horizontal positioned long 20cm, diameter are the cylindrical aluminum rotating cylinder of 7cm, and revolving speed 1200r/min, other spinning parameters are to spin Filament voltage is 6kV, and needle point and rotating cylinder spacing are 13cm, and environment temperature is 20-25 DEG C, relative humidity 20%-30%, to spinning After liquid exhausts, [Tb (BA) is obtained3Phen/PMMA] // [PANI/PMMA] anisotropic conductive green emitting Janus nanobelt battle array Column film；By [the Tb (BA)3Phen/PMMA] // [PANI/PMMA] anisotropic conductive green emitting Janus nanobelt battle array Column film is removed from aluminum rotating cylinder, is cut out to be 3.5cm, perpendicular to nanobelt length direction along Janus nanobelt length direction For the rectangle of 3.0cm, Janus nanobelt is displayed with adhesive tape after being rotated by 90 ° and is fixed on aluminum turn at left and right sides of film On cylinder, the length direction of nanobelt and the axial direction of rotating cylinder are consistent at this time, and the area that left and right sides adhesive tape covers sample is all 3 ×0.25cm2, the area of the Janus nano-band array film of exposing is 3 × 3cm2, as the receiving plane of secondary electrospinning film, spinning solution Dosage and spinning parameter are identical as first time electro-spinning process, secondary electrospinning are carried out, after the completion of spinning by film from aluminum rotating cylinder It removes and is cut, obtain 3 × 3cm2The double anisotropic conductive flexible compound films of green emitting.The double anisotropy of green emitting are led Electric flexible compound film has up-down structure, is combined by upper lower film, the thickness of upper lower film is about 212 μm, in upper lower film, is received Rice strip length direction is vertical, and nanobelt is in aligning, as shown in Figure 1；The double anisotropic conductives of prepared green emitting are soft Janus nanobelt aligns to form array films in property composite membrane, Janus nanobelt with a thickness of 930nm, as shown in Figure 2；Institute The width of Janus nanobelt is 6.64 ± 0.01 μm in the double anisotropic conductive flexible compound films of the green emitting of preparation, sees Fig. 3 It is shown；The distribution of S and Tb element can reflect polyaniline and Tb (BA) respectively3The distribution of phen, S element are distributed only over Janus The side of nanobelt, in the other side of Janus nanobelt, this is consistent Tb Elemental redistribution with the structure of Janus nanobelt, sees figure Shown in 4；The side of single Janus nanobelt includes dark colour polyaniline, and the other side includes colorless and transparent Tb (BA)3phen Complex, as shown in Figure 5；Using 544nm as monitoring wavelength, double anisotropic conductive flexible compound films have at 200-375nm One wide excitation band, peak value can be classified as π → π * transition of ligand, as shown in Figure 6 at 291nm；In the ultraviolet of 291nm Under light excitation, double anisotropic conductive flexible compound films launch the bright green light that main peak is located at 544nm, it corresponds to Tb ion 's5D4→7F5Transition, as shown in Figure 7；Under the ultraviolet excitation of 291nm, double anisotropic conductive flexible compound film transmittings Chromaticity coordinates the value x and y of fluorescence color are respectively 0.2215 and 0.3876, and the fluorescence color of transmitting is green, as shown in Figure 8；Institute In the upper layer and lower layer film of the double anisotropic conductive flexible compound films of the green emitting of preparation, nanobelt length direction is vertical, namely Conducting direction is vertical, strong along nanobelt length direction electric conductivity in upper layer film, and conductance is 1.62 × 10-8S, and along vertical Directly weak in nanobelt length direction electric conductivity, conductance is 1.28 × 10-12S has anisotropic conductive, in lower membrane, edge Nanobelt length direction electric conductivity it is strong, conductance be 1.16 × 10-8S, and along weak perpendicular to nanobelt length direction electric conductivity, Conductance is 1.27 × 10-12S, has anisotropic conductive, and entire composite membrane has double anisotropic conductives；Prepared Composite membrane has the function of good green emitting and double anisotropic conductives.
Certainly, the invention may also have other embodiments, without deviating from the spirit and substance of the present invention, ripe It knows those skilled in the art and makes various corresponding changes and modifications, but these corresponding changes and change in accordance with the present invention Shape all should fall within the scope of protection of the appended claims of the present invention.

Claims (2)

1. the double anisotropic conductive flexible compound films of green emitting, which is characterized in that by [Tb (BA)3phen/PMMA]//[PANI/ PMMA] anisotropic conductive green emitting Janus nano-band array film is combined up and down, by aligning in upper lower film [Tb(BA)3Phen/PMMA] // [PANI/PMMA] Janus nanobelt composition, and nanobelt length direction is vertical, namely conductive Direction is vertical, strong along nanobelt length direction electric conductivity, and along weak perpendicular to nanobelt length direction electric conductivity, have double Anisotropic conductive, prepared composite membrane have the function of good green emitting and double anisotropic conductives, membrane area is 3 × 3cm2。
2. a kind of preparation method of the double anisotropic conductive flexible compound films of green emitting as described in claim 1, feature It is, using double-spinneret electrostatic spinning technique arranged side by side, preparing product is the double anisotropic conductive flexible compound films of green emitting, It the steps include:
(1) precipitation method preparation Tb (BA)3Phen complex
By 1.8650g Tb4O7It is dissolved in 15mL concentrated nitric acid, heating is evaporated to obtain Tb (NO3)320mL dehydrated alcohol is added in crystal, It is configured to Tb (NO3)3Ethanol solution；3.6640g benzoic acid and 1.8000g phenanthroline are added in 200mL dehydrated alcohol It is configured to mixed ligand solution, in the case where being stirred continuously by Tb (NO3)3Ethanol solution be added dropwise to mixed ligand solution In, add dense NH3·H2O adjust pH for 6.5-7.0 between, after being heated to 60 DEG C, react 3h, gained precipitating successively with water with Ethanol washing 3 times, 12h is finally dried at 60 DEG C in drying box, obtains Tb (BA)3Phen complex；
(2) polymetylmethacrylate is prepared
100g methyl methacrylate MMA and 0.1g dibenzoyl peroxide BPO is weighed, is added to reflux unit In 250mL three-necked bottle and stir evenly, by above-mentioned solution 90-95 DEG C at a temperature of be vigorously stirred and be back to solution and have centainly Viscosity stops heating and naturally cools to room temperature after its viscosity is close with glycerol while continuing stirring, later will be above-mentioned Infusion is into test tube, influx height 5-7cm, and 2h is stood after perfusion to invisible spectro solution does not have bubble, then Above-mentioned test tube is transferred in 50 DEG C of drying boxes and places 48h, invisible spectro liquid hardening is transparent solid, finally by drying box Temperature improves to 110 DEG C and keeps the temperature 2h, terminates polymerization reaction, then cooled to room temperature, obtains poly-methyl methacrylate Ester PMMA；
(3) spinning solution is prepared
1.0000g PMMA and 0.15000g Tb (BA) is added in the in the mixed solvent of 12.0000g chloroform and 2.0000g DMF3Phen complex simultaneously stirs for 24 hours, obtains a spinning solution, has the function of green emitting；In 14.0000g chloroform and 2.0000g 1.0000g PMMA is added in the in the mixed solvent of DMF, and stirring 2h obtains uniform colloidal fluid, by 0.3000g aniline and 0.5618g Camphorsulfonic acid is added in above-mentioned colloidal fluid and after stirring 2h, and 0.4411g ammonium persulfate is added and stirs 2h, is then put into solution In 5 DEG C of cold compartment of refrigerator for 24 hours, another spinning solution is obtained, there is conducting function；
(4) [Tb (BA) is prepared3Phen/PMMA] // [PANI/PMMA] anisotropic conductive green emitting Janus nano-band array Film
The 5mL syringe that truncated 12# stainless steel syringe needle is all had using two difference, two stainless pin heads are bent respectively 30 ° of angles keep two needle points closely parallel, and make two on two parallel stainless steel syringe needles using a 1mL plastic spray gun headgear The tip of root stainless steel syringe needle is in the middle section of plastic spray gun head, and two spinning solutions respectively take 3mL to be injected separately into two and infuse In emitter, using perpendicular spray mode, reception device is a horizontal positioned long 20cm, and diameter is the cylindrical aluminum rotating cylinder of 7cm, Revolving speed is 1200r/min, and other spinning parameters are spinning voltage 6kV, and needle point and rotating cylinder spacing are 13cm, and environment temperature is 20-25 DEG C, relative humidity 20%-30%, after spinning solution exhausts, obtain [Tb (BA)3phen/PMMA]//[PANI/ PMMA] anisotropic conductive green emitting Janus nano-band array film；
(5) the double anisotropic conductive flexible compound films of green emitting are prepared
By [the Tb (BA)3Phen/PMMA] // [PANI/PMMA] anisotropic conductive green emitting Janus nano-band array Film is removed from aluminum rotating cylinder, is cut out to be 3.5cm, being perpendicular to nanobelt length direction along Janus nanobelt direction length Janus nanobelt is displayed after being rotated by 90 ° with adhesive tape and is fixed on aluminum rotating cylinder at left and right sides of film by the rectangle of 3.0cm On, the length direction of nanobelt and the axial direction of rotating cylinder are consistent at this time, and the area of left and right sides adhesive tape covering sample is all 3 × 0.25cm2, the area of the Janus nano-band array film of exposing is 3 × 3cm2, as the receiving plane of secondary electrospinning film, spinning solution is used Amount and spinning parameter are identical as first time electro-spinning process, carry out secondary electrospinning, take film from aluminum rotating cylinder after the completion of spinning Under cut, obtain 3 × 3cm2The double anisotropic conductive flexible compound films of green emitting, by [Tb (BA)3phen/PMMA]// [PANI/PMMA] anisotropic conductive green emitting Janus nano-band array film is combined up and down, and the thickness of upper lower film is about 212 μm, by [the Tb (BA) aligned in upper lower film3Phen/PMMA] // [PANI/PMMA] Janus nanobelt composition, The width of Janus nanobelt is 6.64 ± 0.01 μm, with a thickness of 930nm, in the upper layer and lower layer film of composite membrane, nanometer strip length Direction is vertical namely conducting direction is vertical, strong along nanobelt length direction electric conductivity in upper layer film, conductance be 1.62 × 10-8S, and along weak perpendicular to nanobelt length direction electric conductivity, conductance is 1.28 × 10-12S has anisotropic conductive, Strong along nanobelt length direction electric conductivity in lower membrane, conductance is 1.16 × 10-8S, and along perpendicular to nanometer strip length Direction electric conductivity is weak, and conductance is 1.27 × 10-12S, has anisotropic conductive, and there are entire composite membrane double anisotropy to lead Electrically；Under the ultraviolet excitation of 291nm, launch the bright green light that main peak is located at 544nm；Prepared flexible compound film tool There are good green emitting and double anisotropic conductive functions.
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